29 the Extiction of the Dinosaurs from a Chemist's Point Ot View: The

Bollettino della Comunità Scientifica in Australasia Ambasciata d’Italia CANBERRA Agosto 2007 The extiction of the dinosaurs from a chemist’s point ot view: the abnormality of iridium at Gubbio, Italy and Woodside Creeck, New Zealand Rossana Untaru In the last 10 years, thanks to some books, films and cartoons, there has been a real explosion of ‘dinosaur- mania’. People of all ages from all over the world have been affected. What exactly happened 135 million years ago to make the dinosaurs vanish and devastate this planet? I have tried, with my thorough research, to review the scientific literature regarding the event that has triggered this mass extinction. The period is also know as the K-T boundary, and is located at the end of Cretaceous period to Tertiary in the geological time scale as seen in table 1. Table 1: Geological Time Scale Eon Era Period Epoch Abs. Age of Events Age (Ma) Phanerozoic Cenozoic Quaternary Recent 0.01 Mammals Ice age ends Pleistocene 1.6 Ice age begins Humans Tertiary Pliocene 5.3 Scabland Floods Miocene 23.7 Oligocene 36.6 Columbia Basalts Eocene 57.8 Formation of Himalayas Paleocene 66 Extinction of Dinosaurs Mesozoic Cretaceous 144 Jurassic 208 Reptiles Flowering Plants 1st Birds and Mammals Triassic 245 Paleozoic Permian 286 1st Dinosaurs Carboniferou 360 s Devonian 406 1st land plants Silurian 438 1st fish Ordovician 505 Cambrian 570 The K-T boundary is characterized by the second biggest worldwide extinction during which more than 80 % of terrestrial and marine species died. The 20% of survivors included salicaceous pelagic organisms (diatoms, radiolarians), limnetic organisms, terrestrial higher plants, terrestrial mammals mainly small carnivorous, insectivorous, and omnivorous vertebrates (Courtillot, 1999). Many scientists around the world have spent several years of research trying to find answers to what happened at the K-T boundary and their findings can be subdivided into two main theories that had split the scientists involved. The two theories are the asteroid impact theory and the Deccan Traps worldwide volcanism. The debate of K-T impact vs volcanism extinction began at the “Cretaceous-Tertiary Environmental Change” meeting in Ottawa, Canada on 19 May 1981.The two theories debate the extraterrestrial impact vs terrestrial volcanism with abrupt and short duration events vs gradual turnover with iridium peak from extraterrestrial provenience vs volcanic origins, initial ‘nuclear winter’ type environment followed by greenhouse warming vs greenhouse warming effects (leading to damage to reproductive system of animals), and impact-induced acidification of marine waters vs carbon dioxide volcanic exhalation leading to marine acidification. A summary of the effects of an asteroid impact can be seen in figure 1. On the other hand the worldwide volcanism it would have had lasted for several hundreds of years with huge amounts of carbon dioxide vaporised into the atmosphere leading to a severe, global greenhouse warming. 29 Bollettino della Comunità Scientifica in Australasia Ambasciata d’Italia CANBERRA Agosto 2007 Figure 1: Asteroid impact and its effect Asteroid impact theory The theory has been developed in late 1970s by the Alvarez team when Louis Alvarez suggested analysing the amount of iridium content in a clay sample found by his sun Walter Alvarez. The samples have been analysed at the Berkley Laboratories by using a novel technique – neutron activation analysis – and showed iridium levels of 5 ppb. The results were published in 1980 in Science magazine "Extraterrestrial cause for the Cretaceous-Tertiary extinction". Iridium is a metal that normally is found in very low concentrations in Earth’s crust with the exception of few locations around the world such as New Zealand, Italy, and Denmark. Iridium was found in a thin, clay layer deposited between Cretaceous and Triassic Period known as the K-T boundary. The clay layer is quite unique as its texture is different from the strata below and above it and contains the information of a mass extinction episode occurred about 67 million years (Ma) before present (BP). Iridium is a metal situated in group 9, period 6 of the Periodic Table of the elements. It can be found as a free element mainly associated with platinum metals ore or with osmium. It is hard, brittle, and very resistant to corrosion. Normally iridium is depleted in the Earth crust being stored in the Earth’s liquid core. Table 2: Comparison between the concentration of iridium and other elements Element Universe Sun Meteorites Crustal rock (ppb) (ppb) (ppb) (ppb) Iridium 2 2 5.5x102 0.4 Platinum 5 9 103 37 Palladium 2 3 6.7x102 6.3 Iron 1.1x105 1.0x106 2.2x108 6.3x107 From the values in table 2 it can be seen that iridium is found in low concentration 0.4 ppb (parts per billion) compared with another trace metal such as palladium in Earth’s crust but the concentration raises sharply in extraterrestrial objects (meteorites, asteroids, comets). The sties around the world with a positive anomaly 30 Bollettino della Comunità Scientifica in Australasia Ambasciata d’Italia CANBERRA Agosto 2007 iridium concentration have been found at several marine and continental K-T boundary section ssuch as Gubbio, Italy, Steves Klint - Denmark, at seven different sites in New Zealand (Hollis, 2003), Caravaca - Spain, El Kef - Tunisia, Brazos River – US, and near Gubbio – Italy (Courtillot, 1999). According to Heymann et al 1996, at Woodside Creek, New Zealand there is a sharp increase by a factor of 1500 in iridium concentration just below the boundary layer whereas the decrease in the above layer is less sharp. The highest peak found at Woodside Creek was of 197 ng/cm2. The sample analysed by Alvarez team was from the pelagic sedimentary deposits near Gubbio, Italy and was containing a band of brown clay between the Cretaceous limestone and the Tertiary red limestone. Furthermore the Cretaceous limestone was found to contain large amounts of Forminifera globutrucana crustacean fossils (carbonate-producing single-cell animals) but those fossils were absent from the clay layer, and in the red limestone layer few crustacean fossils reappeared but are different from those of the upper Cretaceous. In 1981 Glen Penfield and Antonio Camargo, two petroleum geophysicists, published in “Sky & Teleskope” magazine the finding of a large crater located at Chicxulub in the northwest Yucatan peninsula in Mexico, as seen in figure 2. Figure 2: Chicxulub Location – Yucatan Peninsula at the time of impact. In red other sites where there is an iridium anomaly (Hollis, 2003) From the geophysical data found at the impact basin Sharpton et al, 1996, suggested that the crater has a diameter of less than 200 km and found evidence of impact breccia layer of 300 meters thickness of shocked minerals shock metamorphism with planar deformations in quartz, feldspar, and zircons; fused mineral and whole-mineral melts. In addition they have found as well high concentrations of iridium, rhenium, and osmium suggesting extraterrestrial origins. Bellow this layer was found a unit of melt rock dated by 40Ar/39Ar techniques as 65.07 ± 0.1 Ma old (Swisher et al 1992). Bohor et al 1984 found the presence of extensive grain fracturing, shock mosaic, shifted crystal lattice, glass lamellae and high pressure SiO polymorph as seen in figure 8. Shocked quartz forms as a result of the application of a very high pressure of ~ 10 – 50 kPa. The grains have been found in Italy, Denmark, Spain, north-central Pacific, and New Zealand. Tektites and microtektites are other structure forming during an impact; they can be ejected over large distances. Generally are low water and volatile contents, are black, silicate glass bodies similar to obsidian but with a different chemical composition suggesting meteoritic contamination (Glass, 1990). They have been found to be part of K-T boundary sediments. The impact being aquatic had lead to the formation of tsunami up to 150 meters high disturbing the pelagic sediments. At K-T boundary at Brazos River, Texas (Bourgeois et al, 1988), Beloc, Haiti (Carey et all, 1993) and northeast of Mexico (Smit et all, 1992) have found coarse clastic deposits in contrast with the deep-water fine deposits found bellow and above the coarse layer. Located in Baja California, Mexico it was recognized a Pacific margin stratigraphic sequence. The dating with laser-heating 40Ar/39Ar biotite, hornblende, and plagioclase, pumice lapilli tuff in the middle of the valley fill gave an age of 65.5 +/- 0.6. Also the findings of shocked and liquefied sediments at the same site supported for catastrophic land sliding secondary to bolide impact. (Busby, 2002 and Yip et al, 2002). 31 Bollettino della Comunità Scientifica in Australasia Ambasciata d’Italia CANBERRA Agosto 2007 Analysis by means of High Pressure Liquid Chromatography (HPLC) for fullerenes C60 and C70 that forms during wildfires in K-T clays are consistent with the theory of wildfires developed post-impact (Heymann et al 1996). Deccan Trap Theory Deccan Traps, located in west central India, are considered to be the largest volcanic provinces with an area of almost 500,000 km2 covered by basaltic lava. In 1977 McLean started to look at the perturbation of carbon cycle at the K-T boundary but only in 1979 that he began to associate those perturbation with the Deccan traps. McLean proposed, in 1981, that the Deccan Traps mantle plume volcanism perturbed the carbon cycle at K-T boundary that had as result the mass extinction and iridium release from volcanic fumes (Courtillot, 1999). The eruption started just before the K-T boundary and is thought to have lasted for about 200.000 to 500.000 years. The release of large amounts of volcanic ash, carbon dioxide and other volatiles during an eruption forms acid rain, greenhouse effect, and ozone depletion.

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